Hydrocarbon resins produced using cycloparaffinic diluent



United States Patent 2, 5 HYDROCARBON RESINS PRODUCED USING CYCLOPARAFFINIC DILUENT Morton Fefer, Metuchen, NJ assignoi to Ess'o Research and Engineering Company,- a corporation of Delaware No Drawing. Filed Oct. 31, 1958, Ser. No. 770,940 6 Claims. (Cl. 260-82y This invention relates to the preparation of improved petroleum resins from steam-cracked petroleum streams. More particularly, it relates to a process for preparing resins from steam-cracked light naphtha streams wherein the formation of undesirable insoluble polymer is minimized and the resin quality is improved by carryingout the polymerization in the presence of a cycloparafiinic diluent. V I p 7 Until recently, the petroleum resins of the general type described herein have been produced largely from the steam-cracked heavier petroleum fractions boiling in the range of about 250 to 700 R, such as heavy naphtha, kerosene, gas oil, and the like. These heavier fractions are cracked in the presence of 50-90 niol percent steam at temperatures of about 1000" to 1500 F. to give highly unsaturated products. The liquid out boiling from about 60 F. up to 400 F. and higher, containing large proportions of C to C olefins and diolefins, is then polymerized over a Friedel-Crafts catalyst to produce the desired petroleum resins. The preparation of such resins f has been described in US. Patent 2,734,046 and other patents. I

Now, however, light naphthas are used frequently as steam-cracking feed stocks in place "of the heavier naphthas, gas oils and the like. While the steam cracking of such light naphthas has been quite successful in producing ethylene, butadiene, and the like, there has been considerable difficulty in the preparation of high quality petroleum resins from the C 250 F. fraction obtained from such steam-cracked light naphthas. It has previously been found that the only steam-cracked light naphtha cut attractive for resin production is the C or C -C fraction boiling from about 60 to 120 F. The preparation of satisfactory resins from such a out has been described in copending applications Serial Nos. 627,090 and 734,055.

However, even when the C or C5'C cut is used as the resin feed, there is usually formed during the polymerization an insoluble polymer, or gel, which makes recovery of the resin product diflicult. This gel in the reaction mixture also adversely affects the color, clarity, and other'p'ro'perties of the resin. This gel formation is especially serious in a continuous process, where it causes plugging of the piping in the circulating system.

It is an object of this invention to provide a method for preparing high quality petroleum resins with a minimum of insoluble polymer formation. Another object is to provide a method for preparing petroleum resins of high softening point. It is a further object to provide an efficient continuous process for preparing high quality petroleum resins from steam-cracked light naphtha fractions.

It has now been found that gel formation can be greatly inhibited and the resin softening point improved by polyriterizing the C or C -C steam cracked light naphtha fraction in the presence of a cycloparaflinic hydrocarbon diluent. The cycloparafiinic hydrocarbons which have been found to inhibit gel formation include cyclopentane, 'c'yclohexane, cycloheptane, and the alkyl substituted homologs thereof. Cyclohexane is the preferred diluent.

The diluent may be employed in amounts varying from 5 to 50 wt. percent based on the resin feed. Optimum results are obtained with 10 to 30% of diluent.

2 V n I Either direct addition, where the polymerization catalyst is added to a solution of the resin feed in the aro matic diluent or reverse addition where the resin feed is added to a slurry of the catalyst in the diluent, may be employed.

The resin feeds preferred to use in this invention are obtained by steam-cracking a light naphtha boiling from about 120 to 350 F. in the presence of 50-90 mol percent steam at temperatures of about 1000" to 1500f F. The steam-cracked fraction boiling from about 60 to 120 F. is the suitable resin feed. Optionally, certain components such as cyclopentadienes and Z-methyl butene-l are removed from the resin feed prior to polymerization. The cyclopentadienes, which sometimes tend to degrade the resin color but improve resin softening point,- may be'removed if desired by heat treating the 60120 F. fraction todimerize the cyclopentadienes and then distilling the mixture to remove the dimers". The Z-methyl but ene-l, which degrades the resin softening point, may be removed by careful fractional distillation to remove the 86 to 90 F. fraction.

The above C or C -C steam-cracked naphtha fractions generally have a composition which ranges as follows (in the following formulae R is an alkyl group):

Component Wt. Percent C5 Diolefinsr. 10 to 30 C Olefins:

Type I, OHr=GHR 10 to 30 TypeII, ROH=CHR 10 to 30 it Type III, CH=C 10 to 30.

Type IV, RCH=C\ 3 to 10.

R 0 Paratfins 15 to 40. 06 Compon n 0 to 5.

Of course, any C or C C steam-cracked petroleum fraction boiling within the range of about 60 to F. having a composition within the above ranges, is suitable for this invention; as to olefin types, see U S. Patent 2,625,527, column 2, and C. E. Boord, The science of Petroleum, vol. II, Oxford Univ. Press, p. 1349 (-1938). Forexample, the C cut from a typical steam-cracked C 220 F. Kuwait naphtha, after substantial cyclopentadiene removal, has the following composition.

The polymerization is carried out at temperatures between -40" to 'F., preferably at 75 to 1110 F., using about 0.25 to 3%, preferably 1 to 1.5% of a Friedel-Crafts catalyst such as A101 BF etc., based of; cracked naphtha being treated When the direct addition technique is employed the AlCl catalyst maybe added as a finely divided solid or in solution withasatalyst promoter such as methyl, ethyl, or t-butyl chloride, etc. When reverse addition is used, the resin feed m be added to the slurry or powdered A101, in the diluent 3 which may also contain small amounts of a promoter if desired. The polymerization is usually carried out at atmospheric pressure, but at the higher temperatures it is desirable to increase the pressure suiiiciently to keep to a 1 liter round bottom flask. The admixture was maintained for two hours in the flask at 95 F. The reaction mass was then quenched by adding 20 ml. (10 vol. percent) of a solution of 1 wt. percent Ethofat, a

the monomers in the liquid phase. Accordingly, when 5 nonionic wetting agent, in distilled water, and stirring the polymerizing at 160 F. a pressure of about 5 atmosmixture for about 30 minutes at 95 F. The aqueous pheres is desirable. phase was decanted ofi, the remaining mixture was Upon completion of the reaction the catalyst is deagitated with 20 ml. vol. percent) of 10 wt. percent stroyed by adding water or methyl alcohol or the like. sodiumcarbonate, and the aqueous phase was removed. The catalyst and quenching medium are separated from 10 The crude resin solution was charged to a one liter the resin solution by simple gravity separation, filtration, Claisen flask equipped with a thermometer, and the soluor the like. The resin solution is washed with water, tion was distilled to 392 F. liquid temperature at atmoscaustic, an aqueous solution of sodium carbonate or the pheric pressure. The overhead resin ratfinate was dislike to remove final traces of catalyst. The cycloparaflin carded, and the remaining resin solution was then disdiluent and unreacted naphtha are distilled from the tilled to 518 F. liquid temperature at 5-6 mm. Hg. The resin solution at atmospheric pressure. The liquid polyflask containing the finished resin was weighed for yield mer or fill is finally removed by vacuum distillation. determinations while still hot, after the vacuum had been The desired hydrocarbon resin constitutes the bottoms released. The overhead liquid polymer or fill material from this final distillation. The yield and softening point was recovered and weighed. The hot, finished resin was are largely dependent upon the severity of this final stn'p- 2O poured into a heated ring for softening point determinaping step, with the yield decreasing and the softening tion. point increasing with increased severity of stripping. The results are tabulated in Table I.

Table 1 Run A B O D E F Res1nteed,gm 200.... 300 300 200 300.;-. 200. A101,, m 2 a a a a a. Diluent None. n-heptane. VM&P Varsol... Benzene Oyclohex- Gm 150 100 15o miii Resin Yield, wt. Percent a. 35.3..... 33.7"... 45. owllormatiomwt.Percent .5 6.6 0.4-..." None Resin properties:

Softening Pomt,o. 7o 79 73.5 70 74 86. Color, Gardner 2 1 l 1 1 1.

I Wt. Percent based on resin feed.

The invention will be further illustrated by the following examples.

Unless otherwise designated, all percentages and ratios are given on a weight basis through this applicaiton.

EXAMPLE I A blend of C -C steam-cracked petroleum gas oil fractions, having an initial boiling point of 60 F. and from which the cyclodienes had been substantially removed following a dimerization step, had the following composition:

The above blend was prepared from available steamcracked gas oils to simulate a C fraction of a typical steam-cracked light naphtha stream. It will be noted that the composition of the blend is almost identical to that of the typical steam-cracked Kuwait light naphtha shown hereinbefore.

The above blend was polymerized in this example without a diluent (run A), with n-heptane as a diluent (run B), with VM & P naphtha as a diluent (run C), with Varsol, a partially aromatic solvent, as a diluent (run D), with benzene as a diluent (run E), and with 'cyclohexane as a diluent (run F).

In each run of this example, a portion of the above blend was admixed with aluminum chloride and charged It is readily observed from Table I that the gel formation is considerable when no diluent is used or when a nonaromatic diluent is used. When benzene or cyclohexane is used, on the other hand, the gel formation is negligible. Furthermore, with cyclohexane, both resin yield and softening point are improved considerably.

Having described the general nature and several specific embodiments of the present invention, the true scope is now particularly pointed out in the appended claims.

What is claimed is:

1. A method for producing a petroleum resin from a steam-cracked, light naphtha, petroleum fraction comprising C and C aliphatic hydrocarbons which comprises contacting said petroleum fraction with a Friedel- Crafts catalyst in an amount of about 0.25-3 wt. percent based on the feed fraction in the presence of a liquid cycloparaffinic hydrocarbon diluent, utilized in amount of 5 to 50 wt. percent based on the feed fraction, in a polymerization zone at a temperature between 40 and +160 F. for a period sufficient to produce a high quality petroleum resin.

2. A method for producing a petroleum resin from a steam-cracked, light naphtha, petroleum fraction boiling substantially between 60 and F. which comprises: contacting said petroleum fraction with an aluminum halide catalyst in an amount of about 0.25-3 wt. percent based on the feed fraction and about 10 to 30 wt. percent, based on said petroleum fraction, of a liquid cycloparaffinic hydrocarbon diluent at a temperature between about 40 and F. for a period suflicient to produce a high quality petroleum resin.

3. A method according to claim 2 wherein the diluent is cyclohexane.

4. A method according to claim 2 wherein the diluent is cycloheptane.

5. A continuous method for producing petroleum resins from a steam-cracked light naphtha fraction boiling substantially between 60 and 120 F. and having the following composition:

Wt. Percent Cr dlolefins to 30 C ole Type I CH OHR Type Ii, ROH=CHR R Type III, CH O\ 10 to 30 B Type IV, RUB- C 3 to 10 R C; paratllns to 40 Ce components 0 to 5.

wherein R is an alkyl group, which comprises feeding said fraction, 0.25 to 3.0 wt. percent AlCl, catalyst, and 10 to wt. percent cyclohexane diluent, based on said fraction, to a polymerization zone maintained at a term perature between and F.; passing the resulting polymerization mixture to a quenching zone where the reaction is quenched and the A101 catalyst is separated from said mixture; passing said mixture to a stripping zone where said cyclohexane diluent and unreacted hydrocarbons are stripped firom the polymerization products; passing said products to a vacuum distillation zone where the liquid polymer product is stripped from said products; and recovering the resulting solid petroleum resin product.

6. A method according to claim 5 wherein substantially all the cyclodienes are removed from said fraction prior to polymerization.

References Cited in the file of this patent UNITED STATES PATENTS 1,982,708 Thomas et al. Dec. 4, 1934 2,775,576 Hammer et al. May 20, 1953 2,827,447 Nowlin et a1. Mar. 18, 1958 2,834,768 Friedlander May 13, 1958 2,850,488 Baxter Sept. 2, 1958 

1. A METHOD FOR PRODUCING A PETROLEUM RESIN FROM A STREAM-CRACKED, LIGHT NAPHTHA, PETROLEUM FRACTION COMPRISING C5 AND C6 ALIPHATIC HYDROCARBONS WHICH COMPRISES CONTACTING SAID PETROLEUM FRACTION WITH A FRIEDELCRAFTS CATALYST IN AN AMOUNT OF ABOUT 0.25-3 WT. PERCENT BASED ON THE FEED FRACTION IN THE PRESENCE OF A LIQUID CYCLOPARAFFINIC HYDROCARBON DILUENT, UTILIZED IN AMOUNT OF 5 TO 50 WT. PERCENT BASED ON THE FEED FRACTION, IN A POLYMERIZATION ZONE AT A TEMPERATURE BETWEEN -40* AND +160*F. FOR A PERIOD SUFFICIENT TO PRODUCE A HIGH QUALITY PETROLEUM RESIN. 